Stabilized polyalkylene oxides



United States Patent 3,331,809 STABILIZED POLYALKYLENE OXIDES Otto Mauz,Frankfurt am Main, Germany, assignor to Farbwerke HoechstAktiengesellschaft vormals Meister Lucius & Burning, Frankfurt am Main,Germany, a corporation oi Germany No Drawing. Filed Mar. 30, 1965, Ser.No. 444,058 Claims priority, application Germany, Apr. 10, 1964, F42,576 Claims. (Cl. 260-4535) The present invention relates tostabilized polyalkylene oxides and a process for preparing them.

It is known that homoand copolymers of alkylene oxides, like allpolyethers, are more or less liable to degradation reactions under theaction of light and atmospheric oxygen and therefore, must be stabilizedprior to being processed or used.

It has already been proposed to use aromatic amines or phenols asstabilizers, for example, for polypropylene oxide. However, suchstabilizers are not efiective enough to prevent degradation in thepresence of light and/ or at elevated temperatures.

Now I have found that polyalkylene oxides can be stabilized with phenolsin an advantageous manner by using a mixture consisting of (a) 1 to 5%by weight of a compound of the following Formula I in which R stands foran alkyl radical with 1 to 18 carbon atoms,

(b) 0.1 to 2% by weight of his (4-hydroxy-3-tert.butylin which n is awhole number within the range of 1 to 4, R and R each stand for an alkylradical with 8 to 20 carbon atoms or the group (CH COOR in which groupIn is a whole number within the range of 1 to 4 and R is an alkylradical with '8 to 20 carbon atoms, the above percentage figures beingcalculated on the polymer.

Exemplary of compounds of Formula I to be used in the process of theinvention are 2,4,5-trihydroxy-acetophenone, 2,4,5 trihydroxybutyrophenone, 2,4,5 trihydroxy-valerophenone,2,4,5-trihydroxy-caprophenone, 2,4, 5-trihydroxy-phenyl-octyl-ketone,2,4,5-trihydroxyphenylnonylketone, 2,4,S-trihydroxy-phenyl-decylketone,2,4,5- trihydroxyphenyl-dodecylketone, 2,4,5tn'hydroxyphenylhexadecylketone and 2,4,5trihydroxy-phenyl-octadecylketone.

Exemplary of compounds of Formula II to be used in the process of theinvention are di(dodecyl) sulfide, di (octadecyl) sulfide, di(dodecyl)disulfide, di(octadecyl) disulfide, di(dodecyl) trisulfide,di(octadecyl) trisulfide, di(dodecyl) tetrasulfide, di(octadecyl)tetrasulfide, thiodiglycolic acid dodecyl ester, thiodipropionic acidoctadecyl ester, thiodibutyric acid dodecyl ester, trisulfide (diaceticacid octadecyl ester) and tetrasulfide(diacetic acid octadecyl ester).

The mixtures make suitable stabilizers for polyalkylene oxides. The termpolyalkylene oxides is here intended to mean homoand copolymers ofalkylene oxides which have been obtained by polymerizing saturatedalkylene oxides, for example, ethylene oxide and propylene oxide;substituted epoxides, for example, epichlorhydrin, perfluoropropyleneoxide and 1-chloro-3,4-epoxybutane; cycloaliphatic epoxides, for examplecyclohexene oxide;

3,331,809 Patented July 18, 1967 epoxy ethers, for example methylandphenylglycidyl ethers; or by copolymerization of saturated withunsaturated epoxides, for example, allylglycidyl ether, 0-allylphenylglycidyl ether, glycidyl acrylate, vinylcyclohexenemonoepoxide, cyclohexene oxide, butadiene monoxide, 1,2-epoxyhexene-5,1,2-epoxycyclooctene-(5), the said polymerization or copolymerizationbeing carried out in known manner in the presence of ionic catalysts.

The abovementioned stabilizer mixtures are added to the polymer in solidform or in the form of a solution and then intimately mixed "with thepolymer. The stabilizer mixtures may also be used for stabilizingmixtures of polymers.

The polyalkylene oxides stabilized by the process of the invention maybe used for many fields of application, for example, for the manufactureof shaped articles, films and fibers.

It is also possible to dissolve or swell the abovementioned homoandcopolymers in appropriate solvents or swelling agents. The solutions orswellings shall have a solid content of about 20 to 30%. Examples ofsuitable swelling agents or solvents are dimethyl formamide,tetramethylene sulfone, dioxane, methanol, benzene and other aromaticsubstances, chlorinated hydrocarbons, and donble and triple mixtures ofthe said solvents or swelling agents.

To the solutions or swellings of the copolymers of saturated andunsaturated epoxides which have been stabilized in accordance with theinvention, compounds having a cross-linking action may be added.Suitable cross-linking agents are, for example, sulfur-acceleratorsystems, organic peroxides or other substances forming free radicalsunder cross-linking conditions, for example, azoisobutyric aciddinitrile or azodicarboxylic acid diamide.

It is also possible to add to the solutions or swellingsof the polymersstabilized in accordance with the invention a further substance, forexample, active or inactive soots, light fillers, dyes or pigments,extender oils or lubricants.

The stability of the polyalkylene oxides stabilized by the process ofthe invention was examined as shown in the table given hereinafter.

The following example serves to illustrative the invention but it is notintended to limit it thereto, the parts being by weight.

Example With the use of a copolymer of 92.5 mol percent of propyleneoxide and 7.5 mol percent of allylglycidyl was prepared on a roll millat a temperature of the rolls of about 40 C.

parts of the mixture so obtained were dissolved in, or made into a pastewith 400 parts of methanol, and a mixture of 3% by weight of2,4,5-trihydroxybutyrophenone, 0.5% by weight ofbis(4-hydroxy-3-tert.butyl- 6-methyl-phenyl) sulfide and 0.5% by weightof di(octadecyl) disulfide was added.

With the use of water as the liquid for the precipitating bath, themixture was spun under the following 4 droxy-butyrophenone,2,4,5-trihydroxy valerophenone, 2, 4,5-trihydroxy caprophenone,2,4,5-trihydroXy-phenyloctyl-ketone, 2,4,5-trihydroXyphenyl-nonylketone,2,4,5-

S innin tem erature 20 C. V cinveyigng i 02 gjmin'tnhydroxy-phenyl-decylketone, 2,4,5 tnhydroxyphenyl- Nozzle I 6/300 5dodecylketone, 2,4,5 trihydroxyphenyl-hexadecylketone Titer 6/200 and2,4,5-trihydroxy-phenyl-octadecylketone. Temperatum of precipitatingbath C. 3. The composition according to claim 2 wherein com- Time ofstay in precipitating bath 60 sec. PP l is a member Selected from thegroup Temperature f crOSMinking 1 9 C srsting of di(dodecyl) sulfide,di(octadecyl) sulfide, di Time of ro -li ki i h t d h ft 60 10 (dodecyl)disulfide, di(octadecyl) disulfide, di(dodecyl) Draw-off rate 5 m./min.trisulfide, di(octadecyl) trisulfide, di(dodecyl) tetrasul-After-vulcanization on bobbin 120 sec./ 160 hot air. fide, di(octadecyl)tetrasulfide, thiodiglycolic acid dodecyl TABLE Concentra- After 24hours of After 100 hours of tion of Tensile Elongation exposure to light1 exposure to light Stabilizers stabilizer strength at break in percentin g./den. in percent by weight Tensile Elongation Tensile Elongationstrength at break strength at break in gJden. in percent in gJden. inpercent 2,4,5-trihydroxy-butyrophenone 3 Eittfififiififfffflift???.. 0.5MO 11653 1,590 943 Di(octadecy1) disulfide 0.5Bisthyflroxgfi-(Ii-tezrt.-butyl-6-methyl- 2 9D S11 e Diioctiiecyl)disulfide 2 650 (a) (a) 2,4,5-trihydroxy-butyrophenone 2 4 0. 1, 655

1 Rapid exposing to light of Xenotest lamp (temperature 45 0., relativeatmospheric moisture 30%).

2 Comparison tests. 3 Fiber destroyed.

I claim: 7 V

1. A composition of matter comprising a polyalkylene oxide and a mixtureconsisting of (a) 1 to 5% by weight, calculated on the polymer, of acompound of the following formula in which R stands for an. alkylradical with l to 18 carbon atoms, (b) 0.1 to 2% by weight, calculatedon the polymer, of bis(4-hydroXy-3-tert.butyl-6-methylphenyl) sulfide,and (c) 0.1 to 2% by weight, calculated on the polymer, of a compound ofthe following formula ester, thiodipropionic acid octadecyl ester,thiodibutyric acid dodecyl ester, trisulfide (diacetic acid octadecylester) and tetrasulfide (diacetic acid octadecyl ester 4. Thecomposition according to claim 3 wherein the polyalkylene oxide is amember selected from the group consisting of homopolymers of saturatedepoxides and copolymers of saturated epoxides with unsaturated epoxides.

5. The composition according to claim 1 wherein component (a) is2,4,5-trihydroxy-butyrophenone and component (c) is di(octadecyl)disulfide.

References Cited UNITED STATES PATENTS 2,686,123 8/1954 Campbell et a1.998 2,759,828 8/1956 Bell et al. 99163 2,871,219 1/1959 Baggett et al26045.95 2,871,220 1/ 1959 MacDonald 260-4595 2,934,518 4/ 1960 Smith260-45.9 3,219,623 11/ 1965 Berardinelli 260 -4595 3,235,624 2/1966-Green 260-857 3,277,044 10/1966 Weissemel et al. 260-458.

DONALD E. CZAIA, Primary Examiner. LEON I. BERCOVITZ, Examiner.

V. P. HOKE, Assistant Examiner,

1. A COMPOSITION OF MATTER COMPRISING A POLYALKYLENE OXIDE AND A MIXTURECONSISTING OF (A) 1 TO 5% BY WEIGHT, CALCULATED ON THE POLYMER, OF ACOMPOUND OF THE FOLLOWING FORMULA